Copolymers of 2-halogeno-allyl alcohol or 2-halogeno-allyl esters



Patented Apr. 22, 1947 S PATENT OFF 2,419,221 ICE COPOLYMERS OF Z-HALOGENO-ALLYL ALCOHOL OR 2 HALOGENO ALLYL ESTERS William 0. Kenyon and John H. Van Campen, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation oi New Jersey No Drawing. Application May 11, 1942, a Serial No. 442,453

1 Claim. 1

This invention relates to copolymers of 2-halogeno-allyl alcohols or 2-halogeno-allyl esters.

Z-halogeno-allyl alcohols and 2-halogeno-allyl esters are known, but all attempts to homopolymerize these substances to give useful resinous materials have so far failed.- Certain esters of 2-chloro-allyl alcohol, viz. those containing at least two ethylenic linkages, e. g. 2-chloro-allyl crotonate and di-(2-chloro-allyl) -succinate, have been conjointly polymerized with compounds also containing an ethylenic linkage conjugated with another carbon to carbon double bond such as styrene, to give cross-linked polymers which usually have decreased solubilities in organic solvents. Certain other esters of 2-chloro-ally1 alcohol, containing but one ethylenic linkage, viz. 2-chloro-allyl chloroacetate, have beenproposed as "modifiers in the polymerization of polymerizable organic compounds also containing but one ethylenic linkage, such as vinyl compounds and vinylidene chloride.

We have now found that 2-halogeno-allyl alcohols and 2-halogeno-allyl esters containing but one ethylenic linkage can be copolymerized with polymerizable organic compounds containing an ethylenic linkage cgnjugated with another double-bond linkage, e. g. an ethylenic or carbonylic linkage, to give useful resinou copolymers. Especially useful compounds are obtained with polymerizable organic compounds containing an ethylenic linkage conjugated with a carbonylic linkage, i. e. polymerizable organic compounds containing the group It is, accordingly, an object of our invention to provide new resinous copolymers. Another object is to provide a process for preparing such copolymers. Other objects will become apparent hereinafter.

In accordance with our invention, we copolymerize 2-halogeno-allyl alcohols and 2-halogeno- 1 allyl esters containing but one ethylenic linkage.

with polymerizable organic compounds containing an ethylenic linkage conjugated with another double-bond linkage. As 2-halogeno-allyl compounds, we prefer the more readily available, more stable 2-chloro-allyl compounds. As 2-chloroallyl esters which we have found especially useful in practicing our invention, the following can be mentioned: 2-chloro-allyl esters of monobasic in- -tate the copolymer.

2 acid and (ii-substituted acrylic acids, such as methacrylic acid, ethacrylic acid and a-ChlOlO- acrylic acid, esters of acrylic acids, e. g. methyl acrylate, isobutyl acrylate, methyl methacrylate, n-butyl methyacrylate and methyl cz-ChlOlO- acrylate.

The proportion of monomeric 2-halogeno-allyl compound to polymerizable organic compound containing an ethylenic linkage conjugated with another double-bond linkage can be any desired ratio. However, we have found that in the copolymer the ratio of 2-halogeno-allyl compound to the second compound is never greater than 1:1. More than one 2-halogeno-ally1 compound can be copolymerized with one polymerizable organic compound containin an ethylenic linkage conjugated with another double-bond linkage, and more than one of the compounds containing the conjugated system can be employed with on 2-halogeno-allyl compound. 3

In general, we prepare our new copolymers as follows: the monomers are mixed in the desired ratio, a polymerization catalyst, e. g. an organic peroxide,- added, and the resulting mixture allowed to polymerize, advantageously with warming. Any of the catalysts known to effect the polymerization of vinyl compounds can be employed. The resulting resin is dissolved in a suitable solvent, and the solution poured into a nonsolvent for the resin (usually water) to precipitate the resin. The precipitated resin is then washed with water (and steamed,'if necessary) and finally dried. The following examples and table will serve to illustrate th copolymers and the process for preparing them.

EXAMPLE 1.COPOLYMER or 2-CHLORO-ALLYL ALCOHOL AND METHYL-a-METHACRYLATE A solution of 5 g. of methyl a-methacrylate, 5 g. of 2-chloro-allyl alcohol and 0.05 g. of benzoyl peroxide was prepared and placed in an Erlenmeyer flask. The flask was stoppered and placed in an oven at 40 C. After four and one-half months the mixture was found to be solid and slightly yellow in color. The product was dissolved in acetone and the solution diluted to cc. with acetone. The diluted solution was filtered and then poured into cold water to precipi- The cream colored, fibrous precipitate was soaked for two hours, filtered and dried in the air at room temperature. The yield was 5.2 g. The copolymer contained chlorine equal to 8.27% by weight.

EXAMPLE 2.COPOLYMER or Z-CHLDRO-ALLYL ALCOHOL AND STYRENE A solution of 10.6 g. of styrene, 9.4 g. of 2- chloro-allyl alcohol and 0.2 g. of benzoyl peroxide were sealed in a glass tube and put into. a water bath at 40 C. for fifteen days. The reaction mixture was then diluted with an equal volume oi'dioxane and the diluted mixture poured into 700 cc. of methanol to precipitate the copolymer. The copolymer was dissolved in dioxane and the solution poured into water to precipitate the copolymer. The copolymer was filtered off and dried in the air at room temperature. The colorless, friable product weighed 2.5 g. and contained 2.6% by weight of chlorine.

EXAMPLE 3.-COPOLYMER or 2-CHLORO-ALLYL ALCOHOL AND 2-MErnAcaYLIc Aom A solution of 9.25 g. of 2-chloro-allyl alcohol, 8.6 g. of a-methacrylic acid and 0.2 g. of benzoyl peroxide was heated for thirty minutes in a steam bath. The resulting semi-solid mass was dissolved in acetone containing some water. The acetone solution was poured into distilled water to precipitate the copolymer. The copolymer was permitted to soak for two hours in the water and then was filtered off and dried in the air at room temperature. The slightly yellow, friable product weighed 9.2 g. and contained 7.85% by weight of chlorine,

EXAMPLE 4.--COPOLYMER or 2-CHLORO-ALLYL CHLORIDE AND METHYL or-METHACRYLATE' A solution of 50 g. of methyl methacrylate, 56 g. of 2-chloro-allyl chloride and 1.06 g. of benzoyl peroxide was prepared and heated on a steam bath. After twenty-seven and one-half hours heating, 1.06 g. of benzoyl peroxide were added to the yellow, viscous liquid. At the end of two further hours of heating, the reaction mixture was very viscous. Heating was discontinued and the reaction mixture dissolved in acetone. The acetone solution was poured into hot Water to precipitate the copolymer. The copolymer was then steamed for five hours. The copolymer was redissolved'in acetone and the acetone solution again poured into water to precipitate the copolymer. The copolymer was soaked in ethanol and again dissolved in acetone. The acetone solution was again poured into water to precipitate the copolymer. The copolymer was filtered off and dried at room temperature. The slightly yellow, friable product weighed 75 g. and con tained 28% by weight of chlorine.

EXAMPLE 5.COPOLYMER or 2-CHLoao-ALLYL CHLORIDE AND STYRENE A solution of 9.7 g. of styrene, 10.3 g. of 2-chloroallyl chloride and 0.2 g. of benzoyl peroxide was sealed in a glass tube and the tube immersed in a water bath at 40 C. for fifteen days. The reaction product, a viscous liquid, was diluted with an equal volume of 1,4-dioxane. The resulting solution was poured into 700 cc. of methanol to precipitate the copolymer. The copolymer was permitted to soak in the methanol for some time. The copolymer was then redissolved in dioxane and reprecipitated by pouring the solution into water. The copolymer was filtered ofi and dried in the air at room temperature. The colorless, friable copolymer weighed 5.7 g. and contained 15.49% by weight of chlorine.

EXAMPLE 6.CoPoLYMER' F 2-CHLoxo-ALLYL CHLORIDE AND w-METHACRYLIC Acrn A solution of 11.2 g. of 2-chloro-allyl chloride, 8.6 g. of methacrylic acid and 0.2 g. of benzoyl peroxide was heated for one-half hour in a steam bath. The resulting semi-solid mass was dissolved in acetone containing some water. The copolymer was separated by precipitating the solution into cold water. After soaking for an hour in water, the copolymer was filtered oil, and dried in the air at room temperature. The dried, colorless, friable product weighed 8.8 g. and contained 16.97% by weight of chlorine.

ExAmLE 7.COPOLYMER or 2-CnLoRo-ALLYL ACETATE AND Marmn. ACRYLATI acetone solution poured into water and the precipitated copolymer steamed for five hours. The copolymer was redissolved in acetone, and the acetone solution poured into distilled water to precipitate the copolymer. The copolymer was permitted to soak in the water for some time and was finally filtered from the water. Copolymer was then dried in a desiccator under reduced pressure. The almost colorless copolymer was a bit friable and weighed 20 g. It contained 13.48% of chlorine.

EXAMPLE 8.COPOLYMER or Z-CHLORO-ALLYL ACETATE AND ACRYLIC Acrn ExAMrLE 9.COPOLYMER or Z-CHLoRO-ALLYL ACETATE AND MErHYL ME'rHAcaYLArE A solution of 13.45'g. of2-chloroallyl acetate, 10 g. of methyl methacrylate, and 0.12 g. of benzoyl peroxide was prepared and sealed into a glass tube. The tube and contents "were heated in a water bath at 50 C'. for seventeen days, at the end of which time the product was hazy and' faintly yellow. The copolymerwas dissolved in acetone, the solution filteredgaj'nd the copolymer precipitated into water and soaked several hours in fresh water. It was then, steamed for four hours, redissolved in acetone, precipitated into distilled water, and soaked'in, fresh distilled water. The product was dried-.,in the air at room temperature. The colorless, friable material weighed 17.2 g. and contained 11.97% of chlorine.

EXAMPLE 10 .--CoPoLY1\rn-i i or"- 2-CHLoao-ALLYL ACETATE AND 1STYRENE A solution of 13.45 g. of 2-chloroallyl acetate, 10.4 g. of styrene, and 0.12 g, of benzoyl peroxide was prepared and'sealed into a glass tube. The tube and contents were heated in a water bath at 50 C. for twenty-one days, at the end of which time the product. was very viscous, clear, and yellow in color. It was dissolved in dioxane, poured into distilled water, steamed for four hours, and redissolved in dioxane. This solution was precipitated into distilled water, the copolymer soaked'for three hours, filtered, and dried in the air at room temperature. The colorless, friable product weighed 12.4 g. and contained 7.42% of chlorine.

The following table summarizes some of the more significant copolymerizations which have been carried out in accordance with our invenion.

' copolymer. The copolymer was permitted to soak for some time in the benzene. It was then filtered Table mole ratio 9 {2 I t oilfihiorogramso amso 9 teen aycomchloro-eliyl second monomeric compound, grams enzoyl 223, 853:? c lorlue in pound to compound peroxide polymer second com- I pound in oopolymer 2-OBLORO-ALLYL ALCOHOL COPOLYMERB 9. 26 a-methacrylic acid, 8.6 0. 2 7. 86 1:4. 18 92. 6' m-methacryllc acid, 86. 1. 786 7. 72 1:4. 28 46. 26 a-methacryllc acid, 21.6. 0.68 11. 61 1:2. 48 46. 25 a-methncrylic acid, 21.6. 1. 7 12. 42 1:2. 24 46. 26 a-met hacryiic acid, 21.6. 1. 36 11. 69 1:2. 6 46. 26 a-methacrylic acid. 21.6. 1.36 12 6 1:223 46. 26 a-methacrylic acid, 21.6. 0.68 12.36 1:2. 26 46. 26 a-methncryiic acid, 21.6.... 0. 68 ll. 86 1:2. 41 6. methyl a-mcthacrylate, 6.0 0. 06 R. 27 1:3. 37 46. 3 methyl a-methacrylate, 60. 0. 963 8. 76 1:3. 14 46 methyl-acrylate, 43 0. 89 17. 02 l 1. 36 7. 9 n-butyl a-methacrylate, 12.1. 0.2 6. 47 1 :3. 21 7. 9 n-butyl a-methacrylate, 12.1 0.2 6.12 1:3. 43 9. 4 styrene, 10.6..-.'. 0. 2 2. 6 1:12. 26 v 2-OHLORO-ALLYLOBLORIDE COPOLYMERB 1 ll. 2 a-methacry 12. 86 1:6.13 ll. 2 wmethacry 0. 2 16. 97 1:3. 68 112.0 mmethacry 98 10. 33 1:2. 98 11.1 m-methacry 169 1:36 11. 1 a-m cthacry 01 13. 21 1 :4. 96 66 methyl a-methacrylete, 60 1.06 28 1:1.416 66 methyl acrylnt 0. 99 32. 2 1: l. 21 8. 8 n-butyl methacrylate, 11.2. 0. 2 l7. 0 1:2. 16 ll. 1 styrene, 10.4. 0.107 16.04 1:8. 47 11.1 styren 20.8 0. 0169 40. 11. 28 1:6. 1 10.3 styrene, 9.7 0. 2 40, 16 days 16.49 1:3.84

Z-CHLORO-ALLYL ACETATE COPOLYMERS 26 acrylic acid, 10.7 0. 077 100, 16.6 hr 13. 67 1:1. 46 methyl acryiate. 12.8 0. 078 100, 3 days 13. 48 1:1. 6 13. 6 methyl acryiate, 17.2 0. 07 100, 2 days 9. 68 1:2. 76

can be copolymerized with certain compounds which themselves are not pclymerizable. such, as maleic anhydride. The -rollowing example will serve to illustrate such a copolymer.

Exempt: 11.-Commune or z-cntoao-atrm. Acsrarr: AND Mar-arc ANHYDRIDE To a solution oi 20.1 g. of 2-chloro allyl acetate and 14.7 g. of maleic anhydride at 60 C. were added 0.07 g. of benzoyl peroxide. The resulting solution was heated in an oil bath at 120 C. After five minutes heating, the mixture underwent a slightreaction which quickly stopped. Also .a yellow color appeared. The reaction mixture was cooled somewhat and 0.28 g. of benzovl peroxide were added. The resulting solution was heated in the oil bath at 115 C. After five minutes heating, another vigorous, but short. reaction took place, and at the end or fifteen minutes the heating was stopped. The viscous-amber reaction product was dissolved in acetone, the resultin: solution filtered, and the filtered solution poured into 760 cc. of benzene to precipitate the oil and dried in the air. The slightly yellow triable product-weighed 21.5 g. and was found to.

contain 14.89% of chlorine.

What we claim as our invention and desire to be secured by Letters Patent of the United States is:

A copolymer of 2-ch1oro-allyl acetate and acrylic acid containing 13.67 per cent 01 chlorine.

WILLIAM o. KENYON. JOHN H. VAN CAMPEN. I

nnrnnnncns crrnn The following references are of record in the file oi this patent:

UNITED STATES PATENTS Number Name Date 2,160,941 Britten et al. June 6. 1939 0 2,160,943 Britton et al. June 6, 1939 2,186,360 Britton et a1. Jan. 9, 1940 2,205,390 Britten et al June 25, 1940 2,273,891 Pollack Feb. 24, 1942 2,308,495 D'Alelio Jan. 19, 1943 66 2,334,358 Smith Nov. 16, 1943 2,332,897 D'Aielio Oct. 26, 1943 2,332,900 D'Alelio Oct. 26, 1943 2,332,460 Muskat Oct. 19, 1943 2,388,851 Kenyon et al. Nov. 13, 1946 FOREIGN PATENTS Number Country Date British Oct. 8, 1941 

